KR101219738B1 - Oxynitride phosphor powders, nitride phosphor powders, and preparating method of the same - Google Patents

Abstract

The present application can be used for displays such as vacuum fluorescent displays (VFDs), field emission displays (FEDs), LED displays, or lighting devices such as cold cathode fluorescent lamps (CCFL) and LED lamps, or light emitting devices such as backlights. The present invention relates to a method for producing a nitride-based and nitride-based phosphor powder, and to a method for producing the phosphor powder, wherein the method for preparing the phosphor powder is obtained by nitriding a part or all of the metal oxide through firing in an atmosphere containing nitrogen using a fine carbon material. It includes.

Description

Oxynitride-based phosphor powders, nitride-based phosphor powders, and preparation methods thereof {OXYNITRIDE PHOSPHOR POWDERS, NITRIDE PHOSPHOR POWDERS, AND PREPARATING METHOD OF THE SAME}

The present application relates to a method for producing an oxynitride-based phosphor powder, an oxynitride-based phosphor powder, and a method for producing a nitride-based phosphor powder and a nitride-based phosphor powder thereby.

Phosphors are used in vacuum fluorescent displays (VFD), field emission displays (FED), light emitting diode (LED) displays or LED backlights. In any of these phosphors, excitation energy for exciting the phosphor is required, and the energy is excited by excitation light having high energy such as vacuum ultraviolet ray, ultraviolet ray, electron beam or blue light to generate visible light. However, these phosphors have a problem of long-term exposure to high energy excitation light, deterioration of luminance or deterioration of color rendering index due to heat or moisture generated from the use of the device, thereby causing a problem of so-called fluorescence quenching. There is a need for a phosphor that can be solved.

As one solution to solve the above problems, oxynitride and nitride-based phosphors are used, but the synthesis of such phosphors is mostly performed at a solid state reaction at a high temperature of 1800 to 2000 ° C. and a high pressure of 10 to 100 atm. In addition, since most raw materials start from nitride, expensive equipment and expensive materials are used in the synthesis, and there is a problem in that it is difficult to obtain a uniform phosphor during synthesis. In addition, in order to use the phosphors usefully for the above applications, there is a need for improvement of novel phosphors for efficiently exciting each application and RGB phosphors for high color rendering.

Due to these conventional problems, nitriding methods of nitriding precursors have been attracting attention in the synthesis of oxynitride and nitride phosphors. The nitriding method refers to the use of metals or oxides, not nitrides, as precursors for obtaining nitrides. There are three major nitriding methods: (1) nitriding of metals by Self-Propagating High-Temperature Synthesis (SHS), (2) nitriding using gases and oxides containing nitrogen, and ( 3) Nitrogenation using a gas containing nitrogen, oxides and carbon is typical. This nitriding method has advantages and disadvantages according to each nitriding principle. While the nitriding method of (1) can easily obtain a high purity nitride material, since it requires a high purity metal raw material as a precursor, it is difficult to uniformly mix metals and there is a cost problem. The method of (2) uses the oxide as a precursor to nitrate the oxide through an ammonia gas, typically a gas containing nitrogen as the atmosphere of the reactor. Ammonia decomposes at 800 to 900 ° C. to easily yield nitrides. However, since the method using a gas, the nitriding reaction may proceed only on the surface of the particles and greatly depends on the particle size of the precursor. According to these results, the degree of nitriding of the outside and the inside may be different. In the nitriding method of (3), a mixture of carbon and oxide reacts oxygen of carbon and oxide during firing, and in the process of removing oxygen of oxide in the form of CO, the vacancies of oxygen include nitrogen in the atmosphere. React with to obtain oxynitride and nitride. However, in this process, unreacted carbon remains after the reaction due to carbon particles that are not uniformly mixed, which is a problem. The nitride material thus obtained is used in various applications such as engineering ceramics and optical materials. However, the method of (3) above has a problem that the characteristics of the nitride material can be greatly influenced in the application of optical materials (e.g., fluorescent materials). Have.

In order to solve this problem of the prior art, a small sized precursor having a uniform composition is required. In addition, the conventional method is the cause of the problem from the non-uniformity and the powder of the large particles caused by the mechanical mixing of the large size precursor (μm size). Due to this problem, a nano-sized precursor has recently been used for the nitriding method of (2), and a gas (for example, methane) containing carbon at the same time as the nano-sized precursor has been used for the nitriding method of (3). have. However, this too, nanoscale precursors containing silica are easily vitrified to form coarse particles and form bulk particles, which is a problem.

In order to solve the above problems, the present application is to obtain a precursor of nano-sized uniform composition by using a liquid precursor (LPP = Liquid Phse Precursor) sintering method and to obtain fine carbon materials derived from various organic polymers such as oxides and celluloses. Method for producing oxynitride-based phosphor and nitride-based phosphor by the liquid phase precursor-carbon thermal reduction and nitridation (LPP-CRN) method, and the oxynitride-based phosphor and A nitride-based phosphor powder is provided. Since the present application is based on the liquid phase method by the liquid precursor sintering method, it is possible to obtain and use a uniform nano-sized precursor (a mixture of oxides and carbon), and to include the process of nitriding it by nitriding. It is possible to provide a method for producing oxynitride-based and nitride-based phosphor powders having a uniform particle size distribution, excellent temperature characteristics or luminous efficiency, as well as excellent productivity and economic efficiency, and a phosphor powder thereby.

However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, an aspect of the present application is to impregnate an organic polymer material with an aqueous solution comprising a metal source and a silicon (Si) source for forming an oxynitride phosphor, to obtain a primary precursor, and the 1 Provided is a method for producing an oxynitride-based phosphor powder, comprising firing the primary precursor at a temperature of 800 to 1800 ° C. under a nitrogen-containing atmosphere to obtain an oxynitride-based phosphor powder.

Another aspect of the present application provides an oxynitride-based phosphor powder obtained by the above production method.

Another aspect of the present application is to impregnate an organic polymer material with an aqueous solution comprising a metal source and a silicon (Si) source for forming a nitride phosphor to obtain a primary precursor, and the primary precursor is added under a nitrogen-containing atmosphere to 800 It provides a method for producing a nitride-based phosphor powder comprising firing at a temperature of 1 to 1800 ℃ to obtain a nitride-based phosphor powder.

Another aspect of the present application provides a nitride-based phosphor powder obtained by the above production method.

Another aspect of the present disclosure can provide a display comprising a powder of the oxynitride-based and / or nitride-based phosphor as a phosphor.

Another aspect of the present application provides a lamp comprising a powder of the oxynitride-based and / or nitride-based phosphor as a phosphor.

Provided herein is a novel method for producing oxynitride-based phosphor powders and nitride-based phosphor powders and liquid oxynitride-based phosphor powders and nitride-based phosphor powders produced thereby. The phosphor emits light from blue to red, which can absorb excitation light in the blue or (near) ultraviolet range, and exhibits excellent temperature characteristics or luminous efficiency even at high temperatures.

According to the present application, the carbon balance and control during the manufacturing process of the phosphor powder is started by the impregnated by the impregnation of the organic polymer compound powder (primary precursor) and / or the firing material (secondary precursor) at its low temperature The precursor is evenly mixed with fine residual nm of carbon and an oxide phosphor to enable uniform nitriding. In addition, in the case of the synthesis of the multi-component system, the phosphor of the target composition can be uniformly synthesized through the primary precursor through impregnation in the organic polymer compound and the secondary precursor through the calcined product, and oxynitride through firing in an atmosphere containing nitrogen And nitride-based phosphor powders can be obtained.

1 is an x50 SEM photograph of spherical cellulose (a: particle size 1.5 μm, b: particle size 2.5 μm, c: particle size 3.5 μm) that can be used as an organic polymer in one embodiment of the present application.
Figure 2 is a spherical cellulose particles using a 2.5 ㎛ 1500 ℃, 2 sigan thereby forming a Ca-α-SiAlON obtained according to one embodiment of the present application: FE-SEM photograph of a x5k Eu ^{+ 2.}
Figure 3 according to one embodiment of the present CaAlSiN _3: FE-SEM photograph of a x100k second precursor material for the synthesis of the Eu ^{2 +.}
Figure 4 is a CaAlSiN synthesis for 5 hours and baked at 1600 ℃ in nitrogen 1 cm / s flow line, and a nitrogen atmosphere according to the embodiment of the present _3: Eu ^{2 +} of the XRD pattern.
Figure 5 is a CaAlSiN ₃ synthesis according to one embodiment of the present application: PL (Photoluminescence) of Eu ^{2 +} Spectrum: (a) one here measured by the light-emitting wavelength of 630 nm (excitation) spectrum and (b) an excitation wavelength of 450 nm It is an emission spectrum measured based on.
Figure 6 according to one embodiment of the present nitrogen 1 cm / s and the flow line in a nitrogen atmosphere at 1500 ℃ 5 sigan firing synthesized by Ca-α-SiAlON of: an XRD pattern of Eu ^{2 +.}
7 is Ca-α-SiAlON: Eu ²⁺ synthesized in one embodiment of the present application PL (Photoluminescence) spectrum of the powder: It is a graph of PL (Photoluminescence) of the excitation spectrum (a) measured based on the emission wavelength 582 nm and the emission spectrum (b) measured based on the 400 nm excitation wavelength.
Figure 8 is a composite for 5 hours and baked at 1600 ℃ in the flow line, and a nitrogen atmosphere of nitrogen 1 cm / s in one embodiment of the present β-SiAlON: Eu ^{2 +} of the XRD pattern.
FIG. 9 is 1400 ° C (a), 1450 ° C (b), 1500 ° C (c) and 1500 ° C (d) in an atmosphere of 1 cm / s nitrogen flow rate by LPP-CRN method in one embodiment of the present application; Α-Si ₃ N ₄ Synthesized by Nitriding of SiO ₂ by Firing XRD pattern of the powder.
10 is an XRD pattern of a powder obtained by nitriding of Al ₂ O ₃ at 1400 ° C. (a) and 1500 ° C. (c) by LPP-CRN method in one embodiment of the present application.
11 is of a _{(Ba 0 .95 Eu 0 .05)} 3 Si 6 O 12 N 2 synthesis for 5 hours and baked at 1300 ℃ in the flow line, and a nitrogen atmosphere of nitrogen 1 cm / s in one embodiment of the present XRD Pattern.
12 is a (Ba _{0 .95} Eu _{0 .05)} synthesis according to one embodiment of the present application ₃ Si ₆ O ₁₂ N ₂ Powder PL (Photoluminescence) spectrum: Excitation spectrum (a) measured based on emission wavelength 525 nm and emission spectrum (b) measured based on excitation wavelength 450 nm.
13 is a comparative example, SiO _{2 of} Wuartzs by conventional CRN method XRD pattern of the powder obtained by sintering and nitriding the powder at 1400 ° C. (a) and 1500 ° C. (b).

DETAILED DESCRIPTION Hereinafter, embodiments and examples of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout the specification, when a part is said to "include" a certain component, it means that it can further include other components, except to exclude other components unless specifically stated otherwise.

In one aspect of the present disclosure, an organic polymer material is impregnated with an aqueous solution including a metal source and a silicon (Si) source for forming an oxynitride phosphor to obtain a primary precursor, and the primary precursor is added at 800 ° C under a nitrogen-containing atmosphere. It provides a method for producing an oxynitride-based phosphor powder comprising firing at a temperature of 1 to 1800 ℃ to obtain an oxynitride-based phosphor powder.

In an exemplary embodiment, the method for producing the oxynitride-based phosphor powder, before firing the precursor, pre-fired the primary precursor at a temperature of 150 to 550 ℃ under an oxygen-containing atmosphere to obtain a secondary precursor It may further include, but is not limited thereto.

In an exemplary embodiment, firing in the nitrogen-containing atmosphere may be performed after cooling or continuously after the prefiring, but is not limited thereto.

In an exemplary embodiment, the organic polymer material may be converted into a carbon material in the firing process to act as a reducing agent, but is not limited thereto.

In an exemplary embodiment, the silicon (Si) source may include silica sol or water soluble silica, but is not limited thereto.

In an exemplary embodiment, the particle size of the silica sol may be 5 nm to 50 nm, but is not limited thereto.

In an exemplary embodiment, the metal source for forming the oxynitride phosphor comprises a metal source for forming the oxynitride-based phosphor powder represented by the general formula 1, the production of oxynitride-based phosphor powder Way:

[Formula 1]

(M1 _2a M2 _{1 -a} ) w (M3 _b M4 _{1 -b} ) _x (M4 _c Si _{1 -c} ) _y M4 _d (O _{1 - e} N _{2e / 3} ) _z : R _f ,

In the above formula

M1 is a + monovalent alkali metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), and combinations thereof,

M2 is a + 2-valent alkaline earth metal selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), and combinations thereof,

M3 is a + trivalent metal selected from the group consisting of boron (B), aluminum (Al), yttrium (Y), gadolinium (Gd), terbium (Tb), cerium (Ce), and combinations thereof,

The M4 is +3, +4 or + selected from the group consisting of phosphorus (P), vanadium (V), titanium (Ti), arsenic (As), and combinations thereof, which serve as a parent or study agent of the phosphor. Is a pentavalent metal,

R is a metal selected from the group consisting of europium (Eu), manganese (Mn), cerium (Ce), dysprosium (Dy), samarium (Sm) and combinations thereof as an activator,

A is 0 to 1, w is greater than 0 to 4,

B is 0 to 1, x is 0 to 5,

C is 0 to less than 1, y is greater than 0 to 6,

D is 0 to 3,

E is 0.7 to 1,

Z is greater than 2 and 54,

F is 0.001 (w + x + y + d) to 0.3 (w + x + y + d).

In an exemplary embodiment, the manufacturing method may further include firing at 800 to 1900 ° C. under a pressurized atmosphere of 1 to 100 atm under a nitrogen-containing atmosphere, but is not limited thereto.

In an exemplary embodiment, the organic polymer material may include pulp, crystallized cellulose powder, amorphous cellulose powder, rayon powder, spherical cellulose powder, or cellulose solution, but is not limited thereto.

In an exemplary embodiment, the nitrogen-containing atmosphere may include, but is not limited to, N ₂ , H ₂ / N ₂ mixed gas, or NH ₃ gas.

In an exemplary embodiment, the nitrogen-containing atmosphere may further include CO gas or CH ₄ , but is not limited thereto.

In an exemplary embodiment, the metal source may include, but is not limited to, a flux source.

In an exemplary embodiment, the flux source is NH ₂ (CO) NH ₂ (urea), NH ₄ NO ₃ , NH ₄ Cl, NH ₂ CONH ₂ , NH ₄ HCO ₃ , H ₃ BO ₃ , BaCl ₂ or EuCl ₃ may be included, but is not limited thereto.

In an exemplary embodiment, the method may further include acid treating or alkali treating the oxynitride-based phosphor powder obtained, but is not limited thereto.

Another aspect of the present application provides an oxynitride-based phosphor powder represented by the following general formula 1, wherein the oxynitride-based phosphor powder is prepared by the above production method:

[Formula 1]

(M1 _2a M2 _{1 -a} ) w (M3 _b M4 _{1 -b} ) _x (M4 _c Si _{1 -c} ) _y M4 _d (O _{1 - e} N _{2e / 3} ) _z : R _f ,

In the above formula

M1 is a + monovalent alkali metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), and combinations thereof,

M2 is a + 2-valent alkaline earth metal selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), and combinations thereof,

M3 is a + trivalent metal selected from the group consisting of boron (B), aluminum (Al), yttrium (Y), gadolinium (Gd), terbium (Tb), cerium (Ce), and combinations thereof,

The M4 is +3, +4 or + selected from the group consisting of phosphorus (P), vanadium (V), titanium (Ti), arsenic (As), and combinations thereof, which serve as a parent or study agent of the phosphor. Is a pentavalent metal,

R is a metal selected from the group consisting of europium (Eu), manganese (Mn), cerium (Ce), dysprosium (Dy), samarium (Sm) and combinations thereof as an activator,

A is 0 to 1, w is greater than 0 to 4,

B is 0 to 1, x is 0 to 5,

C is 0 to less than 1, y is greater than 0 to 6,

D is 0 to 3,

E is 0.7 to 1,

Z is greater than 2 and 54,

F is 0.001 (w + x + y + d) to 0.3 (w + x + y + d).

In an exemplary embodiment, the particle diameter of the oxynitride-based phosphor powder may be 15 μm or less, but is not limited thereto.

In an exemplary embodiment, the oxynitride-based phosphor powder may contain M-α-SiAlON: M _Re , β-SiAlON: M _Re , MSi ₂ O ₂ N ₂ : M _Re , EuSi ₂ O ₂ N ₂ , or BCNO. As including, M is at least one selected from the group consisting of Ca, Sr, and Ba, M _Re may be at least one selected from the group consisting of Eu, Ce, Mn and Tb, but is not limited thereto. no.

Another aspect of the present application is to impregnate an organic polymer material with an aqueous solution comprising a metal source and a silicon (Si) source for forming a nitride phosphor to obtain a primary precursor, and the primary precursor is added under a nitrogen-containing atmosphere to 800 It provides a method for producing a nitride-based phosphor powder comprising firing at a temperature of 1 to 1800 ℃ to obtain a nitride-based phosphor powder.

In an exemplary embodiment, the method for producing the nitride-based phosphor powder, before firing the precursor, to pre-fire the primary precursor in an oxygen-containing atmosphere at a temperature of 150 to 550 ℃ to obtain a secondary precursor It may further include, but is not limited thereto.

In an exemplary embodiment, firing in the nitrogen-containing atmosphere may be performed after cooling or continuously after the prefiring, but is not limited thereto.

In an exemplary embodiment, the organic polymer material may be converted into a carbon material in the firing process to act as a reducing agent, but is not limited thereto.

In an exemplary embodiment, the silicon (Si) source may include silica sol or water soluble silica, but is not limited thereto.

In an exemplary embodiment, the particle size of the silica sol may be 5 nm to 50 nm, but is not limited thereto.

In an exemplary embodiment, the metal source for forming the nitride phosphor comprises a metal source for forming the nitride-based phosphor powder represented by the general formula (2):

[Formula 2]

(M1 _2a M2 _{1 -a} ) w (M3 _b ) _x Al _y (M4 _c Si _e N _{4e / 3} ) _z : R _f ,

In the above formula

M1 is a + monovalent alkali metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), and combinations thereof,

M2 is a + 2-valent alkaline earth metal selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), and combinations thereof,

M3 is a + trivalent metal selected from the group consisting of boron (B), yttrium (Y), gadolinium (Gd), terbium (Tb), cerium (Ce), and combinations thereof,

The M4 is +3, +4 or + selected from the group consisting of phosphorus (P), vanadium (V), titanium (Ti), arsenic (As), and combinations thereof, which serve as a parent or study agent of the phosphor. Is a pentavalent metal,

R is a metal selected from the group consisting of europium (Eu), manganese (Mn), cerium (Ce), dysprosium (Dy), samarium (Sm) and combinations thereof as an activator,

A is 0 to 1, w is greater than 0 to 4,

B is 0 to 1, x is 0 to 5,

C is 0 to less than 1, y is greater than 0 to 6,

D is 0 to 3,

E is 0.7 to 1,

Z is greater than 1 to 27,

F is 0.001 (w + x + y + d) to 0.3 (w + x + y + d).

In an exemplary embodiment, the manufacturing method may further include firing at 800 to 1900 ° C. under a pressurized atmosphere of 1 to 100 atm under a nitrogen-containing atmosphere, but is not limited thereto.

In an exemplary embodiment, the organic polymer material may include pulp, crystallized cellulose powder, amorphous cellulose powder, rayon powder, spherical cellulose powder, or cellulose solution, but is not limited thereto.

In an exemplary embodiment, the nitrogen-containing atmosphere may include, but is not limited to, N ₂ , H ₂ / N ₂ mixed gas, or NH ₃ gas.

In an exemplary embodiment, the nitrogen-containing atmosphere may further include CO gas or CH ₄ , but is not limited thereto.

In an exemplary embodiment, the metal source may include, but is not limited to, a flux source.

In an exemplary embodiment, the flux source is NH ₂ (CO) NH ₂ (urea), NH ₄ NO ₃ , NH ₄ Cl, NH ₂ CONH ₂ , NH ₄ HCO ₃ , H ₃ BO ₃ , BaCl ₂ or EuCl ₃ may be included, but is not limited thereto.

In an exemplary embodiment, the obtained nitride-based phosphor powder may further include an acid treatment or an alkali treatment, but is not limited thereto.

Another aspect of the present application, as a nitride-based phosphor powder represented by the general formula 2, provides a nitride-based phosphor powder prepared by the above production method:

[Formula 2]

(M1 _2a M2 _{1 -a} ) w (M3 _b ) _x Al _y (M4 _c Si _e N _{4e / 3} ) _z : R _f ,

In the above formula

M1 is a + monovalent alkali metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), and combinations thereof,

M2 is a + 2-valent alkaline earth metal selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), and combinations thereof,

M3 is a + trivalent metal selected from the group consisting of boron (B), yttrium (Y), gadolinium (Gd), terbium (Tb), cerium (Ce), and combinations thereof,

The M4 is +3, +4 or + selected from the group consisting of phosphorus (P), vanadium (V), titanium (Ti), arsenic (As), and combinations thereof, which serve as a parent or study agent of the phosphor. Is a pentavalent metal,

R is a metal selected from the group consisting of europium (Eu), manganese (Mn), cerium (Ce), dysprosium (Dy), samarium (Sm) and combinations thereof as an activator,

A is 0 to 1, w is greater than 0 to 4,

B is 0 to 1, x is 0 to 5,

C is 0 to less than 1, y is greater than 0 to 6,

D is 0 to 3,

E is 0.7 to 1,

Z is greater than 1 to 27,

F is 0.001 (w + x + y + d) to 0.3 (w + x + y + d).

In an exemplary embodiment, the particle diameter of the nitride-based phosphor powder may be 15 μm or less, but is not limited thereto.

In an exemplary embodiment, the nitride-based phosphor powder is MAlSN: M _Re , M ₂ Si ₅ N ₈ : M _Re , MYSi ₄ N ₇ : M _Re , La ₃ Si ₆ N ₁₁ : M _Re , YTbSi ₄ N ₆ C, or Y ₂ Si ₄ N ₆ C: M _Re , wherein M is at least one selected from the group consisting of Ca, Sr, and Ba, M _Re is one selected from the group consisting of Eu, Ce, Mn and Tb The above may be, but is not limited thereto.

The oxynitride-based phosphor powder and the nitride-based phosphor powder according to the present application may be used in the manufacture of various devices such as displays, lamps, and lighting.

Non-limiting examples of the display include a cathode ray tube, a light emitting diode (LED), a plasma display panel (PDP), a field emission display (FED), or a vacuum fluorescent display (VFD). Can be mentioned.

Hereinafter, the present disclosure will be described in more detail with reference to an embodiment of the method for preparing the oxynitride-based fluorescent substance powder and the method for producing the nitride-based fluorescent substance powder.

In one embodiment of the present application, the method for producing an oxynitride-based or nitride-based phosphor powder, an organic polymer compound containing an aqueous solution containing a water-soluble silica sol as a metal source and a silicon source for forming the oxynitride-based or nitride-based phosphor powder Impregnating to obtain an impregnate (primary precursor), and firing at a temperature of 800 to 1800 ° C. under a condition in which the gas flows at a constant line flow rate under a gas atmosphere containing nitrogen, or the primary precursor is oxygenated. After obtaining the secondary precursor through prefiring at a temperature of 150 to 550 ℃ under an atmosphere containing a continuous or cooling, under a gas atmosphere containing nitrogen at a temperature of 800 to 1800 ℃ under the conditions that the gas flows at a constant flow rate It may include firing with.

The organic polymer compound is converted into a carbon material during the firing process to act as a reducing agent, and the carbon material is in the form of fine particles, which may also serve as a template when preparing oxynitride-based phosphor powders and nitride-based phosphor powders. . For example, given the general formula of the oxynitride-based phosphor powder and the nitride-based phosphor powder to be prepared, the amount of the organic polymer compound is stoichiometrically or in an atomic ratio relative to the number of atoms of the metal elements included in the general formula. By quantitatively calculating and using the quantitatively, nitriding conditions may be controlled during the preparation of each of the oxynitride-based phosphor powder and the nitride-based phosphor powder.

In the case where the silica sol and the metal source are each prepared by using an aqueous solution, these solutions are preferably all acidic or alkaline. The reason is that when a solution having a different pH is used, precipitation occurs, so that impregnation and uniform mixing are difficult.

In the use of the organic polymer compound, the purity of the organic polymer compound is preferably 98% or more, and the organic polymer compound may be a cellulose, for example, a high purity cellulose powder. In addition, the impregnation ratio of the aqueous solution including the cellulose powder and the metal source and the silicon source is preferably 1: 1 to 0.2: 1 wt%. The use of high purity cellulose can reduce impurities, and the impregnation ratio of cellulose and solution increases the residual amount of cellulose-derived carbon when the ratio of cellulose is 1 or more, and acts as an impurity, and if it is lower than 0.2, the amount of carbon for nitriding Shortage. In addition, the atmosphere containing oxygen during the preliminary firing may use air.

In addition, the prefiring to obtain a secondary precursor of the impregnation with the organic polymer, for example, the firing may be carried out at 150 to 550 ℃, or 250 to 350 ℃. On the other hand, the firing time for the remaining amount of carbon can be controlled from 30 minutes to 5 hours for carbon control derived from the organic polymer, which may vary depending on the heating temperature and the amount of the phosphor produced. In addition, when the firing time is less than 30 minutes, the organic polymer compound-derived residual carbon is left in a large amount to reduce the fluorescence properties, and if more than 5 hours, since most of the residual carbon is not oxidized, oxynitride-based and nitride-based phosphors are synthesized. Difficult to do That is, by setting the firing time to 1 to 2 hours as the preferable firing time, the organic polymer compound is converted into residual carbon through the firing step.

When the temperature at which the nitrogen-containing gas and the gas are fired at a constant flow rate is 800 ° C. or lower, the atmosphere containing nitrogen hardly exceeds the activation energy capable of reacting with the precursor material, and thus the reaction is slow. In addition, at the temperature of 1800 ° C. or more, since the material is almost nitrified, it is inefficient for oxynitride-based and nitride-based materials having low diffusion. Preferred temperatures are between 1200 and 1700 ° C. On the other hand, the firing time for producing the oxynitride-based and nitride-based phosphor powder may be 2 hours to 38 hours. This is because the diffusion of the nitride material is considered, and the firing time of 2 hours or less can hardly diffuse and the phosphor that has not diffused for more than 38 hours is not good. Preferred times are from 5 hours to 12 hours.

In addition, in the firing process, the temperature increase rate is performed at 1 to 30 ° C./min. If the temperature is lower than 1 ° C./min, the firing time is long, and the nitriding and oxidation reactions are slow, which is not efficient, and is faster than 30 ° C./min. If it is used, it may cause a breakdown in the equipment used, and it is difficult to obtain a constant phosphor powder because it is difficult to reproduce according to the firing process. In addition, by sintering by rapid firing (RF), a sample can be put into a furnace heated to a temperature for synthesis in a short time to form an atmosphere in which nitrification can occur simultaneously with a carbon pyrolysis reaction. This is a solution to the problem of the interference of the synthesis of high-efficiency oxynitride-based and nitride-based phosphor due to the difference in reaction temperature between the carbon pyrolysis reaction and the gas containing nitrogen and the gas in the atmosphere flowing a certain line flow rate .

In one embodiment of the present application, in the carbonization of cellulose which can be used as an example of the organic polymer compound, in the oxygen-free atmosphere, cellulose is first polymerized by thermal decomposition to combine with the OH of carbon 1 and 6 of the polymer cellulose Breaks the bond and readily converts to Levoglucosan (Levoglucosan: C ₆ H ₁₀ O ₅ ). It can be combined with OH of carbon 1 and 4 of levogluconic acid to be transformed into structural isomers of 3, 6-anhydro-D-glucose (C ₆ H ₁₀ O ₅ ) and 3, 6-anhydro-D-glucose 6 carbon of (C ₆ H ₁₀ O ₅ ) is attached to OH group of 1 carbon to become levoglucose. Levoglucosan and 3,6-anhydro-D-glucose are produced during annealing at the beginning of low temperature and they are composed of three -OH groups and two COs. At higher temperatures, they transform into polymer compounds of various bonds. Typically, carbon 3 and one of 3 -OH groups meet to form 1, 4: 3, 6-dianhydro-D-glucose (C ₆ H ₈ O ₄ ) and its structural isomers. H ₂ O is released per molecule. When this is calcined at a higher temperature, hydrogen of -OH is released, and a conjugate is formed by a strong bond of CO to maintain the form. Thereafter, at a temperature of 800 to 900 ° C. or more, the carbon dioxide disappears and two carbons remain. This can be used to calculate the quantity of carbon.

In addition, through a chemical reaction such as cellulose, the quantitative calculation of carbon required for the preparation of the oxynitride-based phosphor and the nitride-based phosphor powder may be performed from the primary precursor and the secondary precursor. In the method for preparing oxynitride-based and nitride-based phosphors as primary precursors, it is preferable to use cellulose in an amount of carbon for nitriding based on a material capable of self-oxidation as shown in A. Scheme below.

A. Scheme:

2M (NO ₃ ) ₃ + 3C (polymeric compound) + 2N ₂ → M ₂ O ₃ + 6NO ₂ ↑ 3 / 2O ₂ ↑ + 2N ₂ → M ₃ N ₄ + 3CO ↑

The nitriding method using the primary precursor is represented by the starting material (except N ₂ ) of the above A. Scheme, and the amount of carbon can be easily controlled from the organic polymer compound according to the reaction ratio. Can be used. Accordingly, oxynitride-based and nitride-based phosphor powders can be synthesized, respectively.

In addition, the carbon amount control using the secondary precursor can be nitrided as shown in B. Scheme below.

B, scheme:

3MCl ₄ +3 (C ₆ H ₁₀ O ₅ ) + xO ₂ (in air) → 3MO ₂ + 6C + 2N ₂ + 15H ₂ O ↑ + 12CO ₂ ↑ → M ₃ N ₄ + 6CO ↑

B. The above equation is difficult to calculate the amount of carbon because the amount of carbon must be adjusted according to the firing temperature. However, it is possible to reduce the volume of the precursors, thereby increasing the yield, advantageous storage of the secondary precursors and possible intermediate treatments such as flux treatment.

In addition, it is possible to quantitatively control the carbon from the reactions A and B above, and the carbon remaining therein reacts with oxygen of the oxide to be removed by reaction in the form of CO (g) at a temperature of 800 to 900 ° C. It is applied to the production of oxynitride-based and nitride-based phosphor powders.

At this time, the degree of impregnation varies depending on the concentration of the solution, and the concentration of the mixed metal source aqueous solution is 10 to 70 wt%, preferably 25 to 50 wt%, and less than 10 wt%, impregnating the entire polymer compound. The time it takes to become longer and the productivity decreases. In addition, the use of a low concentration of the solution is insufficient in the impregnation of the organic polymer compound as the amount of the solution used increases compared to the organic polymer compound used as a template (template) of the primary precursor. In addition, in the case of the secondary precursor obtained through the prefiring of the primary precursor, the ratio of the solution and the impregnation amount are determined in the process of making the primary precursor, thereby affecting the residual amount of carbon. If the concentration of the solution is 70 wt% or more, the fluidity of the metal source aqueous solution is lowered, which impedes the impregnation process, and a large amount of unimpregnated metal source aqueous solution is hardly absorbed from the surface of the organic polymer compound to the inside of the organic polymer compound. Therefore, the concentration of the mixed metal source aqueous solution is in the range of 25 to 50 wt%, it is preferable that fine particles are uniformly impregnated into the matrix of the organic polymer compound.

The flux may be used as NH ₂ (CO) NH ₂ (urea), NH ₄ NO ₃ , NH ₄ Cl, NH ₂ CONH ₂ , NH ₄ HCO ₃ , H ₃ BO ₃ , BaCl ₂ or EuCl ₃ . Preference is given to using NH ₂ (CO) NH ₂ (urea) as the flux. In addition, the use of flux allows the nitriding reaction to be carried out at lower temperatures and high purity oxynitride-based and nitride-based phosphors can be obtained, respectively. In addition, the flux usage is 1 to 50 wt%, it is difficult to obtain the effect of the flux less than 1% and 50% or more may cause particle coarsening and melting phenomenon due to the excessive use of the flux. Preferred flux usage is 10 to 30 wt%.

For example, the particle size of the silica sol that can be used as the silica source can be vitrified rapidly at a high temperature of less than 5 nm, it is not economical and difficult to use as a sol of 50 nm or more, the particle size of the silica sol is 10-20 nm sol can be used. In addition, water-soluble silica obtained by substituting an organic compound having an OH group in the ethyl group of the TOE from chemical reactions such as TOES (tetraethylorthosilicate), an OH group (eg PG (propylene glycol)) and HCl as a raw material of silica ( WSS: water soluble silicate can be used.

Examples of the metal source include, but are not limited to, chlorides, nitrates, sulfates, phosphates, phosphorus compounds, organometallic compounds, and the like. You can do that. For example, the organometallic compound including the nitrate and the amine group compound (-NH ₂ ) may be preferably used in the synthesis of oxynitride-based and nitride-based phosphors as a compound containing nitrogen. In addition, metal acetate may be used as the organometallic compound, and may react well with the water soluble silicate (WSS), and may also function with the OH group of the compound such as cellulose. The use of the organic polymer compound is crystalline cellulose (purity 99.99%), spherical cellulose powder, liquid cellulose solution, high purity pulp (99.8%) or rayon, preferably high purity pulp. The metal source aqueous solution is absorbed into the fine crystals (40 to 250 Am) of the high purity pulp, and the high purity pulp is completely oxidized in the firing process at about 600 ° C. or higher, disappearing into the atmosphere, and hardly any impurities remain. In addition, these celluloses can react with organic and / or inorganic acids to synthesize acetate-based celluloses such as cellulose acetate and also produce highly reactive celluloses such as Nitrocellulose. In addition, Alkyl-based cellulose, Hydroxyalkyl-based cellulose and Carboxyalkyl-based cellulose can be synthesized using Halogenoalkanes, Epoxides and Halogenated carboxylic acids through inorganic acids to control the impregnation conditions and particle size. In addition, the reaction with the water-soluble silicate to form an inorganic cellulose such as cellulose silicate will be useful for the synthesis of oxynitride and nitride phosphors and the synthesis of silicate phosphors. On the other hand, since the crystalline cellulose powder is in the form of a powder, it is possible to absorb a larger amount of solution during impregnation. For example, spherical cellulose powder of different sizes of Figure 1 (a, b, c) can be adjusted to the particle shape according to the shape and size of the cellulose after synthesis. The FE-SEM photograph of Ca-α-SiAlON, which is an oxynitride phosphor obtained by firing at 1500 ° C. in this manner, is shown in FIG. 2.

Firing in the gas containing nitrogen and the atmosphere in which the gas flows at a constant flow rate is H ₂ / N ₂ = (1 to 50) / (50 to 99) or NH ₃ / N ₂ = (1 to 50) / It may be carried out at (50 to 99) or more easily in an atmosphere containing CH ₃ , CO and SiO, but is not limited thereto. For example, N ₂ / H ₂ (95/5) mixed gas may be used as the reducing atmosphere gas.

In one embodiment of the present application, the oxynitride-based and nitride phosphor powders can be obtained in high purity through further firing in a pressurized atmosphere under a nitrogen-containing atmosphere, for example, the preparation of the oxynitride-based and nitride phosphor powders. The method comprises impregnating a metal source and a silicon source aqueous solution with an organic polymer compound and obtaining a primary precursor and a secondary precursor as described above, or continuously in a gas containing nitrogen and an atmosphere in which the gas flows at a constant flow rate. It is calcined and nitrided at a temperature of 1800 ° C. Afterwards, high purity acid was prepared at a pressure of 1 to 100 atm under a pressure of 1 to 100 atm in an atmosphere containing nitrogen using a pressurized high temperature device (eg, GPS (Gas pressure sintering)) for high purity of the obtained phosphor. Nitride-based and nitride-based phosphor powders are obtained. The pressure is not less than 1 atm of pressure, and 100 atm or more is expensive equipment and inefficient extreme pressure, the preferred pressure is 5 to 20 atm. In addition, the temperature is lower than 1200 ℃ for the diffusion reaction of the nitride and lower than 1900 ℃ is an unnecessary temperature for the diffusion of the nitride. 1600-1800 degreeC is preferable. It is not limited to this.

If necessary, the oxynitride-based and nitride-based phosphor powders obtained in one embodiment of the present application may be subjected to a high purity oxynitride-based and calcination process for removal of residual carbon and impurities at a temperature of 500 to 800 ° C. in an atmosphere containing oxygen, and A nitride phosphor powder can be obtained. The temperature below 500 ℃ is difficult to oxidize carbon. Above 800 ℃, the reduced state of the synthesized oxynitride-based and nitride-based phosphor powders and the mother can be oxidized. To 700 ° C.

Particle sizes of the oxynitride-based and nitride-based phosphor powders produced by the present application may be 15 μm or less, for example, 0.5 to 15 μm, but are not limited thereto.

In one embodiment of the present application, the oxynitride-based phosphor may be represented by the following general formula 1, the nitride-based phosphor may be represented by the following general formula 2, but is not limited thereto:

[Formula 1]

(M1 _2a M2 _{1 -a} ) w (M3 _b M4 _{1 -b} ) _x (M4 _c Si _{1 -c} ) _y M4 _d (O _{1 - e} N _{2e / 3} ) _z : R _f ,

In the above formula

M1 is a + monovalent alkali metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), and combinations thereof,

M2 is a + 2-valent alkaline earth metal selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), and combinations thereof,

M3 is a + trivalent metal selected from the group consisting of boron (B), aluminum (Al), yttrium (Y), gadolinium (Gd), terbium (Tb), cerium (Ce), and combinations thereof,

The M4 is +3, +4 or + selected from the group consisting of phosphorus (P), vanadium (V), titanium (Ti), arsenic (As), and combinations thereof, which serve as a parent or study agent of the phosphor. Is a pentavalent metal,

R is a metal selected from the group consisting of europium (Eu), manganese (Mn), cerium (Ce), dysprosium (Dy), samarium (Sm) and combinations thereof as an activator,

A is 0 to 1, w is greater than 0 to 4,

B is 0 to 1, x is 0 to 5,

C is 0 to less than 1, y is greater than 0 to 6,

D is 0 to 3,

E is 0.7 to 1,

Z is greater than 2 and 54,

F is 0.001 (w + x + y + d) to 0.3 (w + x + y + d).

[Formula 2]

(M1 _2a M2 _{1 -a} ) w (M3 _b ) _x Al _y (M4Si _e N _{4e / 3} ) _z : R _f ,

In the above formula

M1 is a + monovalent alkali metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), and combinations thereof,

M2 is a + 2-valent alkaline earth metal selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), and combinations thereof,

M3 is a + trivalent metal selected from the group consisting of boron (B), yttrium (Y), gadolinium (Gd), terbium (Tb), cerium (Ce), and combinations thereof,

The M4 is +3 selected from the group consisting of phosphorus (P), vanadium (V), titanium (Ti), arsenic (As), carbon (C), and combinations thereof, which serve as a parent or study agent of the phosphor. , +4 or +5 valent metal,

R is a metal selected from the group consisting of europium (Eu), manganese (Mn), cerium (Ce), dysprosium (Dy), samarium (Sm) and combinations thereof as an activator,

A is 0 to 1, w is greater than 0 to 4,

B is 0 to 1, x is 0 to 5,

C is 0 to less than 1, y is greater than 0 to 6,

D is 0 to 3,

E is 0.7 to 1,

Z is greater than 1 to 27,

F is 0.001 (w + x + y + d) to 0.3 (w + x + y + d).

Formula 1 and Formula 2 for the oxynitride-based and nitride-based phosphor powders may include trace amounts of oxygen, which may be oxygen in the crystal, or coordinate oxygen generated by covalent bonds of nitrogen. It can also be Here, the oxygen may have a great influence on the light emission. In general, nitride materials have defects due to covalent bonds, which are easily reacted with oxygen in the air, and thus can be oxidized or coordinated, thereby causing changes in luminescence.

In one embodiment of the present application, it is possible to provide a phosphor powder selected from the group consisting of CASN-based, AlN-based, GaN, TiN, SiN-based, and combinations thereof by the manufacturing method, more specifically M-α -SiAlON: M _Re , β-SiAlON: M _Re , MSi ₂ O ₂ N ₂ : M _Re , EuSi ₂ O ₂ N ₂ , BCNO and MASN: M _Re , M ₂ Si ₅ N ₈ : M _Re , MYSi ₄ N ₇ : Re, La ₃ Si ₆ N ₁₁ : M _Re YTbSi ₄ N ₆ C, Y ₂ Si ₄ N ₆ C: M _Re (M = Ca, Sr, Ba, M _Re = Eu, Ce, Mn, Tb), etc. It is possible to provide a phosphor powder of.

If necessary, in order to remove impurities of a single phase such as AlN generated during the synthesis of the oxynitride-based and nitride-based phosphor powders synthesized by the LPP-CRN method, it is placed in an aqueous solution of 1-10% diluted inorganic acid in Al (OH) _3. In the process of dissolving and removing acid in the form of a higher purity oxynitride-based and nitride-based phosphor powder can be obtained. In addition, the above process is dangerous because it rapidly reacts at a high temperature at a temperature of 0 to 100 ° C., and the inorganic acid may evaporate at a temperature of 100 ° C. or higher, and is not efficient because the reaction proceeds slowly at a temperature below 0 ° C.

If necessary, a pulverization process may be additionally performed on the phosphor powder produced by the above production method. As a device used in the pulverization process, a ball mill, a roller mill, a vibrating ball mill Dry dispersers or ultrasonic dispersers or high pressure arcs, such as attora mills, planetary ball mills, sand mills, cutter mills, hammer mills, jet mills, etc. Any one or more devices of a homogenizer can be used, and the pulverization process through this device can be used to further atomize the phosphor powder.

Hereinafter, an embodiment of the oxynitride-based and nitride-based phosphors of the present application and the oxynitride-based and nitride-based fluorescent materials thereof will be described in detail with reference to the accompanying drawings. However, the present application is not limited thereto.

Nitride based on secondary precursor CaAlSiN ₃ : Eu ^{2 +} Manufacturing

As the metal source aqueous solution of 17.22 g was dissolved in deionized water (Deionized water, DI water) to synthesize a fluorescent substance, 5 g of a composition of _{Ca 0 .92 Eu 0 .08 AlSiN 3} Ca (NO 3) 2 30 wt% aqueous solution A solution comprising 25.67 g of Al (NO ₃ ) ₃ .9H ₂ O 50 wt% aqueous solution, 10.00 g of SiO ₂ (sol) 20 wt% aqueous solution and 3.16 g of EuCl _{3 ·} 6H ₂ O 30 wt% aqueous solution. . The solution was impregnated with 12.26 g of crystalline Cellulose powder to obtain a primary precursor and calcined at 300 ° C. in air to obtain a secondary precursor having a particle size of 20 to 30 nm (FIG. 3). After cooling to room temperature, the mixture was placed in a horizontal tubular electric furnace in which nitrogen flows at 1 cm / s, and calcined at a temperature of 1600 ° C for 5 hours. 4 is an XRD pattern of a nitride phosphor CaAlSiN ₃ : Eu ^{2 +} obtained through the present example. The X-ray pattern is a mixture of a CaAlSiN ₃ : Eu ^{2 +} pattern and an AlN pattern. Figure 5 (a, b) shows the photo luminescence (PL) results obtained through the present application. Figure 5 (a) is a CaAlSiN ₃ with a broad excitation wavelength: Eu ^{+ 2} also shows the properties of the nitride-based fluorescent material 5 (b), it was confirmed that the emission wavelength of the basis of 450 nm.

By primary precursor Oxynitride Ca -α- SiAlON : Eu ^{2 +} Manufacturing

Primary nitriding method according to the metal salt precursor is deionized to obtain the fluorescent material 5 g of the aqueous metal salt solution in the proportion of _{Ca 0 .8 Eu 0 .05 Al 2} .4 Si 9 .6 O 0 .7 N 15 .3 water ( 30% by weight of Ca (NO ₃ ) ₂ , 15.02g Al (NO ₃ ) _{3 ·} 9H ₂ O 50 wt%, 23.40g SiO ₂ (sol ) it was used _{EuCl 3 · 6H 2 O 30 wt} % of 20 wt%, and 0.48 g. The mixed solution was impregnated into 15.48 g of cellulose powder. At this time, the amount of the cellulose was determined using the carbon contained in the cellulose powder by the following reaction formula:

Reaction _{scheme: Ca 0 .8 Eu 0 .05 Al} 2 .4 Si 9 .6 O 23 .675 + 22.975C ( amount of carbon necessary) + 7.65N ₂

_{→ Ca 0 .8 Eu 0 .05 Al} 2 .4 Si 9 .6 O 0 .7 N 15 .3 + 22.975CO ↑ (g)

Since the nitrate raw material of the metal used is a self-oxidizing material without supplying oxygen, it is easy to quantitatively control carbon, and the impregnated solution is 5 ° C. / using a horizontal tube type furnace where nitrogen flows at 1 cm / s. raised to 1500 ℃ min and a heating rate of from 1500 ℃ Ca-α-SiAlON with a timekeeping 5: give the Eu ^{+ 2.} A Ca-α-SiAlON composite:. Eu ²⁺ is XRD analysis (Fig. 6), PL (Fig. 7 (a, b) was evaluated with reference to FIG. 7 (a) is a ^{Ca-α-SiAlON: Eu 2} + of the wide here it shows the wavelength Fig. 6 (b) is a ^{Ca-α-SiAlON: Eu 2} + appears a wide emission wavelength of around 582 nm.

By secondary precursor Oxynitride  β- SiAlON : Eu ^{2 +} Manufacturing

Conducted _{Eu 0 .05 Si 5 Al 0 .95} O 1 .05 N 6 the same method as in Example _2. 5 g of ₉₅ were synthesized. 12.38 g of Al (NO _{3) 3 ·} was used 9H ₂ O 50 wt%, of _{25.38g SiO 2 (sol) 20 wt} % and _{EuCl 3 · 6H 2 O 30 wt} % of 1.00g. This mixed solution was impregnated into 14.61 g of cellulose powder. The firing in the gas containing nitrogen of the said Example and the atmosphere in which the gas flows by a constant line flow was baked at 1600 degreeC for 5 hours at the line flow rate of 1 cm / s in the atmosphere of nitrogen. The synthesized β-SiAlON: Eu ^{2 +} was confirmed by XRD analysis (FIG. 8).

LPP - CRN of SiO ₂ of nitrification

Calculate the carbon of SiO ₂ sol and cellulose to obtain Si ₃ N ₄ 5g powder by LPP-CRN method, impregnating 31.25 g of SiO ₂ 20 wt% (sol) and 17.33 g of cellulose powder at 60:40 wt% Thereafter, using a box-type furnace, firing was performed at 1400 ° C., 1450 ° C. and 1500 ° C. for 5 hours at a line flow rate of 0 cm / s in an atmosphere of N ₂ . The obtained powder is shown in Figure 9 through the XRD pattern analysis. As shown in Fig. 9 (a, b, c), the Si ₃ N ₄ powder at 1400 ° C the temperature is raised to 1400 ° C, 1450 ° C and 1500 ° C the crystallinity of the phases is improved. This is a general nano-size effect can be seen that the reactivity and reaction rate is excellent. In addition, as a result of experimenting with N ₂ wire flow rate as 1 cm / s, it is shown in Figure 9 (d). It was confirmed that nitriding at a flow rate of 1 cm / s improved crystallinity than nitriding at 0 cm / s.

By primary precursor LPP - CRN of Al ₂ O ₃ of nitrification

To obtain 5g of AlN powder by LPP-CRN method, 65.37g of Al (NO ₃ ) ₃ 9H ₂ O 70 wt% solution was calculated by impregnating carbon of 14.83g of cellulose powder to 66:34 wt%, and then in the form of a box. The furnace was fired at 1400 ° C. and 1500 ° C. for 5 hours at a line flow rate of 0 cm / s in an N ₂ atmosphere. The obtained powder is shown in Figure 10 through the XRD pattern analysis. As shown in FIG. 10, at 1400 ° C., AlN powder was mixed with an Al ₂ O ₃ oxide and AlN nitride at 1400 ° C. FIG. On the other hand, when the temperature is 1500 ℃ to form a single phase of AlN.

By secondary precursor ( Ba _{0 .95} Eu _{0 .05} ) ₃ Si ₆ O ₁₂ N ₂ Manufacturing

Example 1, in the same way _{(Ba 0 .95 Eu 0 .05)} 3 Si 6 O 12 N 2 5 g was synthesized. Thus, 24.06 g of Ba (NO ₃ ) ₂ 20 wt%, 7.5 g of SiO ₂ (sol) 40 wt%, and 0.22 g of EuCl _{3 ·} 6H ₂ O 50 wt% of the solution were stirred at a temperature of 70 ° C. for 3 hours to obtain a uniform solution. The solution was prepared. The homogeneous solution was impregnated with 15.89 g of cellulose powder and calcined at 450 ° C. for 1 hour in air. The firing in the gas containing nitrogen of the said Example and the atmosphere in which the gas flows by a constant line flow was baked at 1300 degreeC for 5 hours at the line flow rate of 1 cm / s in the atmosphere of nitrogen. In the case of oxynitride-based phosphors containing less nitrogen, nitriding with a primary precursor is easy. If a small amount of nitriding is required, the amount of high molecular compound to be supplied as a carbon source is too small to impregnate. Therefore, the solution and the amount of the polymer compound is 1: 0.5, and the amount of the oxynitride-based phosphors after the impregnation is less, depending on the amount of nitrogen was calcined at a high temperature (between 250 to 550 ℃). The synthesized (Ba _0.95 Eu _0.05 ) ₃ Si ₆ O ₁₂ N ₂ was evaluated by XRD analysis (FIG. 11) and PL (FIG. 12 (a, b)) measurements. Figure 12 (a) shows a broad excitation wavelength of 450 nm with a focus on the _{(Ba 0 .95 Eu 0 .05)} 3 Si 6 O 12 N 2. Figure 12 (b) is _{(Ba 0 .95 Eu 0 .05)} 3 Si 6 O 12 N 2 appears a wide emission wavelength of around 525 nm.

[ Comparative example  One]

Normal CRN of SiO ₂ of nitrification

Si ₃ N ₄ via normal CRN method To obtain 5 g of powder, SiO ₂ powder on 1 μm quartz and 1 μm C powder were mixed at 60:40 wt% for 24 hours using a ball mill, followed by 0 using a box-type furnace in N ₂ atmosphere. It was baked at 1400 ° C. and 1500 ° C. for 5 hours at a line flow rate of cm / s. The obtained powder is shown in Figure 13 (a, b) through XRD pattern analysis. As shown in FIG. 13, the SiO ₂ powder of the quartz phase is increased in temperature to 1400 ° C. (FIG. 13 (a)) and 1500 ° C. (FIG. 13 (b)), and the crystallinity of the phases is lowered. In the general carbon pyrolysis method, the N ₂ wire flow rate was supplied at 1 cm / s, whereas since the experiment was at a flow rate of 0 cm / s, no nitriding reaction occurred and only the carbon pyrolysis reaction occurred above 900 ° C.

As mentioned above, the present invention has been described in detail by way of examples, but the present invention is not limited to the above embodiments, and may be modified in various forms, and within the technical spirit of the present invention, there is a general knowledge in the art. It is obvious that many variations are possible by the possessor.

Claims (40)

An aqueous solution comprising a metal source and a silicon (Si) source for forming an oxynitride phosphor is impregnated into the organic polymer material to obtain a primary precursor,
Firing the primary precursor at a temperature of 800 to 1800 ° C. under a nitrogen-containing atmosphere to obtain an oxynitride-based phosphor powder
/ RTI >
Wherein the organic polymer material comprises pulp, crystallized cellulose powder, amorphous cellulose powder, rayon powder, spherical cellulose powder, or cellulose solution,
Method for producing oxynitride-based phosphor powder.
The method of claim 1,
Before firing the primary precursor, further comprising prefiring the primary precursor at a temperature of 150 to 550 ° C. under an oxygen-containing atmosphere.
The method of claim 2,
Firing under the nitrogen-containing atmosphere is carried out after cooling after the prefiring or continuously.
The method of claim 1,
The organic polymer material is converted to a carbon material in the firing process to act as a reducing agent, a method for producing an oxynitride-based phosphor powder.
The method of claim 1,
Wherein the silicon (Si) source comprises a silica sol or water-soluble silica, a method for producing an oxynitride-based phosphor powder.
The method of claim 5, wherein
The particle size of the silica sol is 5 nm to 50 nm, the method for producing an oxynitride-based phosphor powder.
The method of claim 1,
The metal source for forming the oxynitride phosphor comprises a metal source for forming the oxynitride-based phosphor powder represented by the general formula 1 below,
[Formula 1]
(M1 _2a M2 _1-a ) w (M3 _b M4 _1-b ) _x (M4 _c Si _1-c ) _y M4 _d (O _1-e N _{2e / 3} ) _z : R _f ,
In the general formula 1,
M1 is a + monovalent alkali metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), and combinations thereof,
M2 is a + 2-valent alkaline earth metal selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), and combinations thereof,
M3 is a + trivalent metal selected from the group consisting of boron (B), aluminum (Al), yttrium (Y), gadolinium (Gd), terbium (Tb), cerium (Ce), and combinations thereof,
The M4 is +3, +4 or + selected from the group consisting of phosphorus (P), vanadium (V), titanium (Ti), arsenic (As), and combinations thereof, which serve as a parent or study agent of the phosphor. Is a pentavalent metal,
R is a metal selected from the group consisting of europium (Eu), manganese (Mn), cerium (Ce), dysprosium (Dy), samarium (Sm) and combinations thereof as an activator,
A is 0 to 1, w is greater than 0 to 4,
B is 0 to 1, x is 0 to 5,
C is 0 to less than 1, y is greater than 0 to 6,
D is 0 to 3,
E is 0.7 to 1,
Z is greater than 2 and 54,
F is 0.001 (w + x + y + d) to 0.3 (w + x + y + d).
The method of claim 1,
And firing the oxynitride-based phosphor powder at a pressure and a temperature range of 1 to 100 atm and 800 to 1900 ° C. in a nitrogen-containing atmosphere.
delete The method of claim 1,
The nitrogen-containing atmosphere is a method for producing an oxynitride-based phosphor powder containing N ₂ , H ₂ / N ₂ mixed gas or NH ₃ gas.
11. The method of claim 10,
The nitrogen-containing atmosphere is a method for producing an oxynitride-based phosphor powder further comprises CO gas or CH ₄ .
The method of claim 1,
The metal source comprises a flux source (flux source), the method of producing an oxynitride-based phosphor powder.
13. The method of claim 12,
Wherein the flux source comprises NH ₂ (CO) NH ₂ (urea), NH ₄ NO ₃ , NH ₄ Cl, NH ₂ CONH ₂ , NH ₄ HCO ₃ , H ₃ BO ₃ , BaCl ₂ or EuCl ₃ , Method for producing oxynitride-based phosphor powder.
The method of claim 1,
A method of producing an oxynitride-based phosphor powder further comprising acid treatment or alkali treatment of the obtained oxynitride-based phosphor powder.
An oxynitride-based phosphor powder represented by the following general formula 1, wherein the oxynitride-based phosphor powder prepared by the method according to any one of claims 1 to 8 and 10 to 14:
[Formula 1]
(M1 _2a M2 _1-a ) w (M3 _b M4 _1-b ) _x (M4 _c Si _1-c ) _y M4 _d (O _1-e N _{2e / 3} ) _z : R _f ,
In the general formula 1,
M1 is a + monovalent alkali metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), and combinations thereof,
M2 is a + 2-valent alkaline earth metal selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), and combinations thereof,
M3 is a + trivalent metal selected from the group consisting of boron (B), aluminum (Al), yttrium (Y), gadolinium (Gd), terbium (Tb), cerium (Ce), and combinations thereof,
The M4 is +3, +4 or + selected from the group consisting of phosphorus (P), vanadium (V), titanium (Ti), arsenic (As), and combinations thereof, which serve as a parent or study agent of the phosphor. Is a pentavalent metal,
R is a metal selected from the group consisting of europium (Eu), manganese (Mn), cerium (Ce), dysprosium (Dy), samarium (Sm) and combinations thereof as an activator,
A is 0 to 1, w is greater than 0 to 4,
B is 0 to 1, x is 0 to 5,
C is 0 to less than 1, y is greater than 0 to 6,
D is 0 to 3,
E is 0.7 to 1,
Z is greater than 2 and 54,
F is 0.001 (w + x + y + d) to 0.3 (w + x + y + d).
The method of claim 15,
An oxynitride phosphor powder having a particle diameter of 15 μm or less of the oxynitride phosphor powder.
The method of claim 15,
The oxynitride-based phosphor powder includes M-α-SiAlON: M _Re , β-SiAlON: M _Re , MSi ₂ O ₂ N ₂ : M _Re , EuSi ₂ O ₂ N ₂ , or BCNO, wherein M is At least one selected from the group consisting of Ca, Sr, and Ba, M _Re is at least one selected from the group consisting of Eu, Ce, Mn and Tb, oxynitride-based phosphor powder
A display comprising the oxynitride-based phosphor powder according to claim 15.
The method of claim 18,
The display is a cathode ray tube, a light emitting diode (LED), a plasma display panel (PDP), a field emission display (FED) or a vacuum fluorescent display (VFD).
Lamp comprising the oxynitride-based phosphor powder according to claim 15.
An aqueous solution comprising a metal source and a silicon (Si) source for forming a nitride phosphor is impregnated into the organic polymer material to obtain a primary precursor,
Firing the primary precursor at a temperature of 800 to 1800 ° C. under a nitrogen-containing atmosphere to obtain a nitride-based phosphor powder
/ RTI >
Wherein the organic polymer material comprises pulp, crystallized cellulose powder, amorphous cellulose powder, rayon powder, spherical cellulose powder, or cellulose solution,
Method for producing nitride-based phosphor powder.
22. The method of claim 21,
Before calcining the primary precursor, further comprising pre-firing the primary precursor at a temperature of 150 to 550 ° C. under an oxygen-containing atmosphere.
23. The method of claim 22,
Firing under the nitrogen-containing atmosphere is carried out after cooling after the prefiring or continuously.
22. The method of claim 21,
The organic polymer material is converted to a carbon material in the firing process to act as a reducing agent, a method for producing a nitride-based phosphor powder.
22. The method of claim 21,
The silicon (Si) source comprises a silica sol or water-soluble silica, the method for producing a nitride-based phosphor powder.
The method of claim 25,
The particle size of the silica sol is 5 nm to 50 nm, the method for producing a nitride-based phosphor powder.
22. The method of claim 21,
Method for producing a nitride-based phosphor powder, wherein the metal source for forming the nitride phosphor comprises a metal source for forming the nitride-based phosphor powder represented by the following general formula (2):
[Formula 2]
(M1 _2a M2 _1-a ) w (M3 _b ) _x Al _y (M4 _c Si _e N _{4e / 3} ) _z : R _f ,
In the general formula 2,
M1 is a + monovalent alkali metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), and combinations thereof,
M2 is a + 2-valent alkaline earth metal selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), and combinations thereof,
M3 is a + trivalent metal selected from the group consisting of boron (B), yttrium (Y), gadolinium (Gd), terbium (Tb), cerium (Ce), and combinations thereof,
The M4 is +3, +4 or + selected from the group consisting of phosphorus (P), vanadium (V), titanium (Ti), arsenic (As), and combinations thereof, which serve as a parent or study agent of the phosphor. Is a pentavalent metal,
R is a metal selected from the group consisting of europium (Eu), manganese (Mn), cerium (Ce), dysprosium (Dy), samarium (Sm) and combinations thereof as an activator,
A is 0 to 1, w is greater than 0 to 4,
B is 0 to 1, x is 0 to 5,
C is 0 to less than 1, y is greater than 0 to 6,
D is 0 to 3,
E is 0.7 to 1,
Z is greater than 1 to 27,
F is 0.001 (w + x + y + d) to 0.3 (w + x + y + d).
22. The method of claim 21,
Calcining the nitride-based phosphor powder at a pressure and a temperature range of 1 to 100 atm and 800 to 1900 ° C. in a nitrogen-containing atmosphere.
delete 22. The method of claim 21,
The nitrogen-containing atmosphere is a method for producing a nitride-based phosphor powder, which comprises N ₂ , H ₂ / N ₂ mixed gas or NH ₃ gas.
22. The method of claim 21,
The nitrogen-containing atmosphere is a method of producing a nitride-based phosphor powder further comprises CO gas or CH ₄ .
22. The method of claim 21,
The metal source comprises a flux source (flux source), the method of producing a nitride-based phosphor powder.
33. The method of claim 32,
Wherein the flux source comprises NH ₂ (CO) NH ₂ (urea), NH ₄ NO ₃ , NH ₄ Cl, NH ₂ CONH ₂ , NH ₄ HCO ₃ , H ₃ BO ₃ , BaCl ₂ or EuCl ₃ , Method for producing nitride-based phosphor powder.
22. The method of claim 21,
A method of producing a nitride-based phosphor powder further comprising acid treatment or alkali treatment of the obtained nitride-based phosphor powder.
A nitride phosphor powder represented by the following general formula (2), wherein the nitride phosphor powder prepared by the method according to any one of claims 21 to 28 and 30 to 34:
[Formula 2]
(M1 _2a M2 _1-a ) w (M3 _b ) _x Al _y (M4 _c Si _e N _{4e / 3} ) _z : R _f ,
In the general formula 2,
M1 is a + monovalent alkali metal selected from the group consisting of lithium (Li), sodium (Na), potassium (K), and combinations thereof,
M2 is a + 2-valent alkaline earth metal selected from the group consisting of magnesium (Mg), calcium (Ca), strontium (Sr), barium (Ba), zinc (Zn), and combinations thereof,
M3 is a + trivalent metal selected from the group consisting of boron (B), yttrium (Y), gadolinium (Gd), terbium (Tb), cerium (Ce), and combinations thereof,
The M4 is +3, +4 or + selected from the group consisting of phosphorus (P), vanadium (V), titanium (Ti), arsenic (As), and combinations thereof, which serve as a parent or study agent of the phosphor. Is a pentavalent metal,
R is a metal selected from the group consisting of europium (Eu), manganese (Mn), cerium (Ce), dysprosium (Dy), samarium (Sm) and combinations thereof as an activator,
A is 0 to 1, w is greater than 0 to 4,
B is 0 to 1, x is 0 to 5,
C is 0 to less than 1, y is greater than 0 to 6,
D is 0 to 3,
E is 0.7 to 1,
Z is greater than 1 to 27,
F is 0.001 (w + x + y + d) to 0.3 (w + x + y + d).
36. The method of claim 35,
A nitride phosphor powder having a particle diameter of 15 µm or less.
36. The method of claim 35,
The nitride-based phosphor powder may be MAlSN: M _Re , M ₂ Si ₅ N ₈ : M _Re , MYSi ₄ N ₇ : M _Re , La ₃ Si ₆ N ₁₁ : M _Re , YTbSi ₄ N ₆ C, or Y2Si4N ₆ C: as including M _Re, wherein M is Ca, Sr, and is at least one selected from the group consisting of Ba, M _Re is one or more nitride-based phosphor powder is selected from the group consisting of Eu, Ce, Mn and Tb.
A display comprising the nitride based phosphor powder according to claim 35.
The method of claim 38,
The display is a cathode ray tube, a light emitting diode (LED), a plasma display panel (PDP), a field emission display (FED) or a vacuum fluorescent display (VFD).
A lamp comprising the nitride-based phosphor powder according to claim 35.

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